JPS62149648A - Production of secondary amine - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by reacting an alcohol or aldehyde with a primary amine in the presence of a catalyst, consisting of three metal components containing copper and nickel and further a small amount of a platinum group element of group VIII metal added thereto and capable of exhibiting high activity and selectivity under pressure while removing water. CONSTITUTION:An alcohol or aldehyde having a straight or branched chain or polyhydric alcohol is reacted with a primary amine in the presence of a catalyst, consisting of three metal components (preferably 1:9-9:1 molar ratio of copper to nickel and at 0.001-0.1 molar ratio of the platinum group element of group VIII metal to the total amount of the copper and nickel) and prepared by adding the platinum group metal catalyst, e.g. platinum, palladium, ruthenium, rhodium, etc., to the copper and nickel at 150-250 deg.C under atmospheric pressure - 5atm pressure (gauge pressure) removing water formed by the reaction to afford the aimed secondary amine. The primary amine is preferably present in a larger amount than the consumption of the alcohol or aldehyde in the system at all times.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a corresponding secondary amine by reacting an alcohol or aldehyde with a primary amine.

Aliphatic secondary amines are used as rust inhibitors, surfactants, bactericides,
As a dyeing aid for fibers and as an intermediate such as a soft base,
It is an industrially important substance.

[Conventional technology]

BACKGROUND ART Conventionally, methods for producing corresponding amines by reacting alcohols or aldehydes with ammonia or primary amines or secondary amines are well known. However, by reacting alcohol etc. with amine etc.
It has been difficult to selectively obtain specific amines, especially secondary amines. That is, regarding the method of producing the corresponding tertiary amine from alcohol and amine, JP-A-52-196404 (copper chromite catalyst, cobalt catalyst) and JP-A-53-59602 (copper-molybten, copper -tungsten catalyst), U.S. Patent No. 3.223,7
There are reports such as No. 34 (Raney nickel catalyst, copper chromite catalyst) and German Patent Application Publication No. 1 493.781 (supported nickel catalyst, supported cobalt catalyst). However, these catalysts have a tertiary effect due to their activity and selectivity characteristics.
Since secondary amines are selectively provided, it is difficult to selectively produce secondary amines.

[Problem that the invention seeks to solve]

Although conventional catalysts are effective for producing tertiary amines due to their characteristics, they are not necessarily effective for selectively producing secondary amines.

In other words, in the reaction between alcohols and primary amines, in conventional methods using catalysts, due to the characteristics of the catalyst, in order to increase the reaction activity, the amount of catalyst must be increased, the reaction temperature must be raised, or the reaction temperature must be increased. Operations such as increasing the pressure are being performed.

In addition, in order to suppress the formation of undesirable side reactants or to prevent the decomposition of primary amines, primary amines are introduced in gaseous form, and excessive amounts of primary amines are added to the reaction system. It was necessary to perform an operation that would prevent this from happening. In this reaction, because the primary amine has two active hydrogens in its molecule, tertiary amines tend to be produced selectively, and in conventional methods using catalysts, the activity and selectivity of the catalyst is low. Due to the insufficiency, it has been difficult to produce secondary amines in high yield and quality. In order to produce high-yield, high-quality secondary amines, it is necessary to suppress the by-product of tertiary amines in this reaction. Even if a primary amine that can be reacted with and that easily generates a tertiary amine is present in excess, it does not decompose or produce a tertiary amine as a by-product, and selectively gives a secondary amine. Catalytic properties that exhibit high activity and high selectivity are required.

[Means for solving problems]

Therefore, as a result of intensive studies to solve these problems, the present inventors developed a new catalyst consisting of a three-component metal consisting of copper and nickel with a small amount of Group 8 platinum group element added.
We were able to solve these problems all at once. That is, the present inventors improved the dehydrogenation and hydrogenation functions required of the catalyst in producing secondary amines by reacting alcohols or aldehydes with primary amines,
In addition, we aim to achieve higher activity and selectivity by selectively generating secondary amines, and explore new functions and properties through intermetallic composites of copper, nickel, and various tertiary component metal species. I did it.

As a result, the present inventors found that by adding a Group 8 platinum group element as a third component metal to copper and nickel as a catalyst metal composition, the combined effect of copper, nickel, and Group 8 platinum group element three component metals was achieved. As a result, we discovered a new function that shows high activity and high selectivity in small amounts, which was not possible with the copper-nickel two-component system.

In other words, as a result of searching for new functions by combining copper, nickel, and a third component metal, the eighth
It has been found that among the platinum group elements, platinum, palladium, ruthenium, and rhodium in particular exhibit extremely effective functions in the reaction of the present invention. In particular, as a third component metal, only such Group 8 platinum group elements exhibit new functions when combined with copper and nickel, and as other third component metals,
For example, the addition of chromium, iron, zinc, zirconium, manganese, cobalt, etc. had no effect (no effect was observed, rather, the result was a reduction in the catalytic function. Three component metals of copper, nickel, and Group 8 platinum group elements) It was discovered for the first time that new catalytic properties that cannot be obtained with other metal compositions are developed through the interaction between them, leading to the present invention.

That is, in the present invention, when producing a secondary amine by reacting an alcohol or an aldehyde with a primary amine, a copper-nisochelium-Group 8 platinum element catalyst is used, and the reaction is carried out in the presence of this catalyst. The reaction is carried out at a temperature of 150°C to 250°C at atmospheric pressure or below 5 atm (gauge pressure) while continuously or intermittently removing the produced water from the reaction system to produce secondary amines in high yield. This method is characterized by manufacturing.

In order to obtain a high yield of secondary amine during the reaction, the reaction must be carried out in such a way that the primary amine is always present in the system in an amount greater than the consumption amount of alcohol or aldehyde per unit time. is preferred.

That is, a method in which the primary amine is added continuously or intermittently under certain conditions so that the amount of alcohol or aldehyde present in the system is greater than that consumed per unit time, or after the reaction temperature is reached. A method in which the primary amine is added to the alcohol or aldehyde all at once, a method in which a mixture of the alcohol or aldehyde and the primary amine is reacted, and a method in which the alcohol is continuously added to the primary amine. Any method such as the above may be used, and essentially, under the reaction conditions (reaction temperature, amount of catalyst, pressure), primary amine exists in the system in an amount greater than the amount of alcohol or aldehyde consumed per unit time. Just let it happen. Although it is possible to carry out the reaction by adding the primary amine in an amount less than this amount (for example, adding it continuously in small amounts), it is necessary to is not desirable.

In the reaction using the catalyst of the present invention, the activity selectivity of the catalyst is excellent, so even if there is an excess of primary amine in the reaction system, its decomposition is unlikely to occur, and the generated secondary amine It exhibits high selectivity in that the reaction between alcohol and aldehyde is inhibited.

In terms of reaction conditions, a pressurized system of 5 kg/cm"C or more can be used, but atmospheric pressure to 5 kg/cm"G can sufficiently achieve the purpose.

In the method of the present invention, the catalyst is highly active, so the reaction conditions are mild, and the process can be carried out with light equipment, and the amount of catalyst used is very small, so the reaction can be completed in a short time. I can do it. In addition, the previously presented special public
It exhibits several times higher activity than the copper-nickel catalyst described in No. 55704, and has extremely excellent reaction selectivity. Therefore, the desired secondary amine can be obtained in high yield and with few side reactions, resulting in high quality secondary amine. In addition, the composite of the three components of copper, nickel, and group 8 platinum group elements increases the durability of the catalyst compared to conventional catalysts, and the activity of the catalyst does not decrease even if it is collected and reused several to dozens of times. It has unique characteristics.

The catalyst of the present invention exhibits extremely high activity and selectivity compared to conventional catalysts, so it is possible to react at low temperatures and at normal pressure, reducing the amount of catalyst required and improving reaction selectivity. As a result, high-yield and high-quality secondary amines can be obtained from branched aliphatic alcohols or aldehydes, from which conventional techniques have not been able to obtain the corresponding secondary amines in high yields. became possible to manufacture. In addition, it has become possible to produce the corresponding secondary amine in extremely high yield even from polyhydric alcohols, which are generally difficult to produce due to secondary amine yield and quality concerns due to the occurrence of side reactions.

The catalyst used in the present invention essentially contains copper, nickel, and Group 8 platinum group elements (hereinafter abbreviated as platinum group elements), and the proportions of copper, nickel, and platinum group elements in the catalyst metal composition used. can be taken arbitrarily.

That is, the molar ratio of the metal atoms of copper and nickel is preferably in the range of 1:9 to 9:1, and the amount of platinum group elements added to the total amount of copper and nickel is in the range of 0.001 to 0.1 (
molar ratio) is preferred.

Platinum group elements particularly suitable for this reaction are platinum, palladium, ruthenium, and rhodium.

Although the three components of copper, nickel, and platinum group elements are essential as the catalyst metal composition, the catalyst suitable for the present invention can be selected from various forms.

That is, in the present invention, when the three components of copper, nickel, and platinum group elements are present in the reaction system as a catalyst composition, the effect due to the interaction between these three components is exhibited for the first time. The composition has an essential catalytic function, and when an alcohol and an amine are reacted, catalytic activity is first expressed by reducing each metal component in a hydrogen atmosphere. Therefore, the difference in the form of the metal before the reduction operation and the state in the system after the reduction operation is not particularly limited in the present invention, and in the method described in the present invention, copper and nickel are Any form is acceptable as long as the interaction between the metal and the platinum group element is exhibited.

Therefore, the forms of metals that are compatible with the method of the present invention include: 1) Forms that can be dispersed in the reaction medium, such as these metals, their oxides or hydroxides, and mixtures thereof; or 2) a mixture of copper, nickel, and platinum group elements each supported on a suitable support, or a mixture of copper, nickel, and platinum group elements supported uniformly on the same support;
Those in a form that are dispersed in the reaction medium 3) Alternatively, they become a metal colloid in the reaction medium, such as aliphatic carboxylates of these metals or complexes stabilized with appropriate ligands, and are homogeneously dispersed in the reaction medium. 4) A mixture of a form that becomes dispersed in the reaction medium as in 1) to 2) and a form that becomes homogeneous in the reaction medium as in 3). Alternatively, it may be in a dispersed form before hydrogen reduction and become uniform after hydrogen reduction, and the three component metals that are the essence of the present invention can be reduced by a reduction operation in a hydrogen atmosphere. It is sufficient if the interaction between the three components is expressed.

In the method of the present invention, more preferable forms of the catalyst include stabilization of the catalyst metal, that is, immobilization of the active surface;
In addition, from the viewpoint of durability against catalyst poisoning substances, it is preferable to have these three component metals uniformly supported on a suitable carrier.

When the three component metals of copper, nickel, and platinum group elements of the present invention are supported on a carrier, suitable carriers include those commonly used as catalyst carriers, such as alumina, silica alumina, diatomaceous earth, silica, and activated carbon. , natural and artificial zeolites, etc. can be used. Although the amount of catalyst metal supported on the support can be arbitrarily determined, it is usually in the range of 5 to 70%.

Various methods can be selected for supporting these three component metals on the carrier surface. In this case, the catalyst raw metal may be oxides or hydroxides of copper, nickel, and platinum group elements, or various metal salts thereof. For example, chlorides, sulfates, nitrates, acetate aliphatic carboxylates of copper, nickel, and platinum group elements, or complexes of these metals, such as acetylacetone complexes and dimethylglyoxime complexes of copper, nickel, and platinum group elements, etc. Further, regarding platinum group elements, carbonyl complexes, amine complexes, phosphine complexes, etc. can also be used. When producing a catalyst using these metal raw materials by supporting them on a carrier, for example, the carrier is thoroughly impregnated with a solution of appropriate salts of copper, nickel, and platinum group elements, and then dried and calcined. Method (impregnation method) The carrier is mixed thoroughly with an aqueous solution of copper, nickel, and an appropriate salt of a platinum group element, such as copper nitrate, 2.7K nitrate, and a platinum group element chloride, and then carbonated. A method in which metal salts are precipitated on a carrier by adding an alkaline aqueous solution such as sodium, sodium hydroxide, or aqueous ammonia (coprecipitation method), or ion exchange of copper, nickel, and platinum group elements with sodium, potassium, etc. on zeolite. There are conventional methods such as the ion exchange method, and the method of heating and melting copper, nickel, platinum group elements, and aluminum metal, cooling and solidifying it to form an alloy, and eluting the aluminum in the alloy with caustic soda (alloy method). Any known method may be used. In the case of impregnation method and coprecipitation method,
After metal deposition, rinse thoroughly with water, dry at around 100℃,
A catalyst is obtained by firing at a temperature of 00°C to 700°C.

In addition, by such a method, only copper or only copper and nickel are supported on a carrier, and before the reaction, nickel or platinum group element supports, aliphatic carboxylates, or complexes are added. In the reaction medium under hydrogen atmosphere,
A method of combining copper with nickel and platinum group elements is also effective.

More preferably, the catalyst form is such that the three components are uniformly supported on the same carrier.

These three components, copper, nickel, and platinum group elements, are essentially essential to the present invention, and the addition of metals other than these three components in small amounts will not have any effect on changing the properties of these three component metals. For addition of large amounts, please refer to these 3.
This is not preferable because it adversely affects the interaction of component metals.

Furthermore, it has been found that the absence of any of the three components of the catalyst composition of the present invention has an adverse effect on the reaction of the present invention.

The alcohol or aldehyde that is the raw material used in the present invention is a linear or branched urea having a number of 8 to 36
saturated or unsaturated aliphatic alcohols or aldehydes, such as 2-ethylhexyl alcohol, octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, etc. and mixed alcohols thereof, also obtained by the Ziegler process Alcohols having a branched chain such as Ziegler alcohol, oxo alcohol obtained by oxo synthesis, and Guerbet alcohol, and examples of the aldehyde include lauryl aldehyde, oxo aldehyde, and other aliphatic aldehydes corresponding to the above alcohols.

Various polyhydric alcohols can also be used.

Examples include 1.3-butanediol, 1,4-butanediol, 1.5-bentanediol, 1.6-hexanediol, and polyhydric alcohols such as diethylene glycol, triethylene glycol, and propylene glycol. Other alcohols include aromatic alcohols such as benzyl alcohol, polyoxyether alcohols such as ethylene oxide or propylene oxide adducts of aliphatic alcohols, and amino alcohols such as ethanolamine and jetanolamine.

The alcohol or aldehyde is particularly an aliphatic alcohol or aldehyde selected from saturated or unsaturated linear or branched aliphatic alcohols or aldehydes having 8 to 36 carbon atoms, and aliphatic glycols having 2 to 12 carbon atoms. is preferred. The amines to be reacted with these alcohols or aldehydes include saturated or unsaturated linear or branched aliphatic primary amines having 4 to 36 carbon atoms, such as butylamine, 2 - Various primary amines such as ethylhexylamine, octylamine, laurylamine, oleylamine, stearylamine, and behenylamine are mentioned.

In the present invention, the alcohol or aldehyde and the first
It is an essential requirement to take out of the reaction system the water produced by the reaction with the amine, and if the produced water is not taken out of the system, the catalyst performance of the present invention cannot be fully exhibited. That is, the catalyst activity and selectivity are reduced, and secondary amines cannot be easily obtained in high yield. Removal of water may be carried out intermittently or continuously during the reaction, as long as the produced water does not exist in the reaction system for a long time and is removed appropriately. It is desirable to remove it. Specifically, hydrogen gas can be recycled by introducing an appropriate amount of hydrogen gas into the reaction system during the reaction and condensing and separating the produced water in a condenser. It is also possible to add a suitable solvent to the reaction system and remove the produced water by azeotropic distillation with this solvent.

In the method of the present invention, a catalyst that has been reduced in advance with hydrogen gas may be used, but the unreduced catalyst is placed in a reactor together with the reaction raw material alcohol, aldehyde, or primary amine, and hydrogen Reduction is carried out by raising the temperature to the reaction temperature while introducing gas or a mixed gas of hydrogen gas and a small amount of gaseous amine. That is, the copper of the present invention
Ninokeru Group 8 platinum group element catalyst has a remarkable feature in that it has a low reduction temperature and can be reduced during the process of heating up to the reaction temperature.

Embodiments of the method of the present invention will be briefly described.

Alcohol or aldehyde or primary amine as a raw material and a catalyst are placed in a reaction vessel equipped with a tube for introducing hydrogen and amine, alcohol or aldehyde, a condenser for condensing and separating water produced by the reaction, and a separator. Prepare.

Although any amount of catalyst can be charged, since the catalyst of the present invention has high activity, the amount is usually in the range of 0.1% to 2% by weight based on the charged alcohol, aldehyde, or primary amine. After replacing the inside of the system with nitrogen gas, temperature rise is started while introducing hydrogen gas. The reaction temperature is usually 180~
The reaction is carried out at about 230°C, but temperatures outside this range can be used depending on the type of reaction. During this temperature rise, the catalyst is reduced and becomes an active catalyst. After reaching a predetermined temperature, an amine is introduced, or an alcohol or aldehyde is introduced into the amine, or a reaction is initiated as a mixture of the primary amine and the alcohol or aldehyde. During the reaction, water produced is discharged from the reaction system together with gaseous substances and a small amount of oily substances, and is separated from the oily substances through a condenser and a separator. The separated oil is returned to the reactor. In addition, as a result of analyzing gaseous substances, it was found that most of these gaseous substances contained by-products (e.g. hydrocarbons,
It has been proven that the catalyst of the present invention has high selectivity because it does not contain amine by-products generated by disproportionation of raw amine, and these gaseous substances can be specially purified by using a circulation machine. It was found that it can be reused without any process.

By directly distilling or filtering the reaction product after the reaction is complete, the secondary amine can be obtained in extremely pure form.

The primary amine used may be equimolar to the alcohol or aldehyde, or may be in excess or in deficiency. That is, an extremely high-quality secondary amine can be obtained simply by removing unreacted primary amine in the former case, and unreacted alcohol or aldehyde in the latter case, as the first distillation fraction.

〔Example〕

The present invention will be explained in detail with reference to the following examples and comparative examples.

Example 1 and Comparative Examples 1 and 2 A three-way catalyst of copper-Ninoker-platinum group element supported on synthetic zeolite was prepared by a coprecipitation method.

The precipitate was filtered, washed with water, dried, and then calcined at 500°C to obtain a catalyst.

Next, using this catalyst, a reaction was carried out using alcohol as a branched chain alcohol and laurylamine as a primary amine. For comparison, copper-nickel binary components and copper-platinum group element binary components were prepared using the same method.
A similar reaction was carried out using a catalyst consisting of the following components.

300 g of Guerbet alcohol (carbon number 20) and 3.0 g (based on alcohol: 1.0%) of the above catalyst were charged into 11 flasks equipped with a condenser to separate water produced by the reaction, and the system was poured with stirring. The atmosphere was replaced with nitrogen, and the temperature was started to increase.

When the temperature reaches 100℃, use a flow meter to supply hydrogen gas at 101/h.
The temperature was raised to 190°C. At this temperature, laurylamine (equal mole to alcohol) 2
The mixture was introduced into the reaction system under atmospheric pressure at a flow rate of 5 mole%/h/1 mole of alcohol, and the reaction was monitored using the amine value and gas chromatography.

The results are shown in Table-1.

Table 1 *Catalyst: Supported amount 50% **Others: Unreacted primary amine, alcohol, by-product 3
As a result, in the two-component copper/nickel and copper/platinum group element catalyst systems of Comparative Examples 1 and 2, the reaction activity between such branched chain alcohols and primary amines was extremely low, and secondary amines, etc. The yield of grade amine was poor.

On the other hand, it was found that the catalyst system of the present invention (Example 1) exhibited extremely high activity and could produce the corresponding secondary amine (alkyl group asymmetric) in high yield.

Examples-2 to 4. Comparative Examples 3 to 7 Next, a reaction between Guerbet alcohol (20 carbon atoms) and a primary amine (14 to 18 carbon atoms) derived from tallow fatty acid was carried out using a catalyst consisting of copper, nickel, and a third component metal. The same method as in Example 1 was used to examine the effects of various third component metal species in the catalyst. The results are shown in Table-2.

Table-2 Reaction temperature = 200°C1 Primary amine addition: 2Qmole%/h to alcohol 1
Equimolar addition of catalyst: Cu/Ni/third component = 8/210.04
(Molar ratio) As a result, it was found that the three-component catalyst system of copper/nickel/platinum group element of the present invention can produce secondary amines with extremely high activity and high selectivity.

On the other hand, as the third component metal, Fe + Z n
It was found that in the system in which t Z r +Cr, Co, etc. were added, the reaction activity and secondary amine selectivity were significantly reduced.

Examples 5 to 10 Next, using the catalyst of the present invention, various alcohols or aldehydes were reacted with various primary amines in the same manner as in Example-1. The results are shown in Table-3.

Table-3 *1 Oxo alcohol: carbon number 12-13 Branching rate 9
4% book 2 molecular weight 400 Reaction temperature: 190°C, reaction time 6 hours, catalyst amount: 1wt
% to alcohol-alcohol grade amine 2 to 1.1 times the mole of alcohol/aldehyde Cu/Ni/third component = 4/110.04 (mole ratio) From the above results, the copper/nickel/platinum group element catalyst of the present invention By using linear or branched alcohol or aldehyde and polyhydric alcohol, 1
It has been found that corresponding secondary amines can be produced from primary amines with high activity and selectivity.

Examples 11 to 14 Next, various reaction methods were used to investigate the reaction between lauryl alcohol and lauryl amine. Display the results -
4.

Table-4 Reaction temperature: 190°C, catalyst: Cu/Ni/Ru=4/110.04
(Mole ratio) to alcohol 065% Reaction time 26 hours (Example-12 is the composition at 12 hours) Molar ratio: equivalent mole of it-class amine to alcohol or more,
In the method of continuously adding the primary amine little by little as in Example 12, tertiary amine is likely to be produced;
Under these conditions, secondary amines are added using a method (Example 11.13.14) in which primary amines are added in an amount equal to or higher than the alcohol consumption rate (consumption amount per unit time) in the system. It has been found that it is possible to selectively produce

Claims (1)

[Claims] 1. Alcohol or aldehyde and primary amine,
In the presence of a copper-nickel-Group 8 platinum group element catalyst, the reaction is carried out at a temperature of 150°C to 250°C under atmospheric pressure or an increased pressure of 5 atm (gauge pressure) or less, while removing water produced by the reaction. A method for producing a secondary amine, characterized by: 2. The method for producing a secondary amine according to claim 1, wherein the Group 8 platinum group element is one or more selected from platinum, palladium, ruthenium, and rhodium. 3. The molar ratio of copper and nickel metal atoms in the copper-nickel-group 8 platinum group element catalyst is 1:9 to 9 for copper:nickel.
:1, and the mole ratio of the Group 8 platinum group element to the total of copper and nickel is 0.001 to 0.1. Production method. 4. A patent characterized in that the reaction between an alcohol or aldehyde and a primary amine is carried out in such a way that the primary amine is present in the system in an amount greater than the consumption amount of the alcohol or aldehyde per unit time. A method for producing a secondary amine according to claim 1 or 2.